Halopropargyl compounds, compositions, uses and processes of preparation

ABSTRACT

Compounds of the formula ##STR1## wherein A is selected from the group consisting of (1) phenyl, (2) naphthyl, (3) phenyl substituted with one or more halo, cyano, (C 1  -C 4 ) alkyl, nitro, (C 1  -C 4 )haloalkyl, and (C 1  -C 4 )thioalkyl, (4) naphthyl substituted with one or more halo, cyano, (C 1  -C 4 )alkyl,nitro,(C 1  -C 4 ), and (C 1  -C 4 ) thioalkyl, (5) thiophene, (6) furan, (7) thiophene substituted with one or more substituents selected from halo and nitro, and (8) furan substituted with one or more substituents selected from halo and nitro; 
     R disclose as microbicidally and fungicidally active.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to control of microorganisms.

2. Description of the Prior Art

Certain classes of iodopropargyl compounds have been proposed asfungicides or microbicides but no compound within those classes hasachieved commercial success.

U.S. Pat. No. 4,616,004 to Edwards discloses fungicidal activity forcompounds of the formula ##STR2##

U.S. Pat. No. 4,639,460 to Rose shows compounds of the formula ##STR3##as fungicides

U.S. Pat. No. 4,520,023 to Schmitt shows3-(3-iodopropargyl)benzo-1,2,3-triazolin-4-ones and their use asmicrobicidal agents.

There was no suggestion in the prior art that compounds within theformula of the present invention would have utility in controllingmicroorganisms.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide new compounds forcontrolling microorganisms.

A further object is to provide methods of making such compounds, methodsof using them, compositions comprising such compounds, and uses of suchcompositions.

These objects, and others which will become apparent from the followingdisclosure, are achieved by the present invention which comprises in oneaspect compounds of the formula ##STR4## wherein A is selected from thegroup consisting of (1) phenyl, (2) naphthyl, (3) phenyl substitutedwith one or more halo, cyano, (C₁ -C₄)alkyl, nitro, (C₁ -C₄)haloalkyl,and (C₁ -C₄)thioalkyl, (4) naphthyl substituted with one or more halo,cyano, (C₁ -C₄)alkyl, nitro, (C₁ -C₄)haloalkyl, and (C₁ -C₄)thioalkyl,(5) thiophene, (6) furan, (7) thiophene substituted with one or moresubstituents selected from halo and nitro, and (8) furan substitutedwith one or more substituents selected from halo and nitro;

R is selected from the group consisting of hydrogen, (C₁ -C₄)alkyl andsubstituted or unsubstituted phenyl wherein the substituents areselected from one or more halo, cyano, (C₁ -C₄)alkyl, nitro, (C₁-C₄)haloalkyl, and (C₁ -C₄)thioalkyl;

R¹ is selected from the group consisting of (C₁ -C₄)alkoxy; hydrogen;optionally substituted phenyl wherein the phenyl substituents areselected from the group consisting of halo, cyano, (C₁ -C₄)alkyl, nitro,(C₁ -C₄)haloalkyl, and (C₁ -C₄)thioalkyl; (C₁ -C₈)alkyl; and optionallysubstituted heterocycles wherein said heterocycles are selected from thegroup consisting of thiophene, furan, imidazole, and triazole, which areoptionally substituted with (C₁ -C₃)alkyl, halo, and nitro; and

X is selected from the group consisting of I and Br.

In another aspect the invention comprises a method of preparing suchcompound comprising reacting a compound of the formula ##STR5## with aniodating or brominating agent.

A further aspect comprises a composition comprising the compounds, orthe compound itself, to protect a material selected from the groupconsisting of wood, paint, adhesive, glue, paper, textile, leather,plastics, cardboard, lubricants, cosmetics, food, caulking, feed andindustrial cooling water from microorganisms.

DETAILED DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENT

The compounds of the invention are of formula I as set forth above. Themore preferred embodiments are the following compounds:

1. N'-Methoxycarbonyl-N'-3-bromopropargyl 4-chlorobenzaldehyde hydrazone

2. N'-Formyl-N'-3-bromopropargyl 4-chlorobenzaldehyde hydrazone

3. N'-Methoxycarbonyl-N'-3-iodopropargyl benzaldehyde hyrazone

4. N'-Methoxycarbonyl-N'-3-iodopropargyl 4-methylbenzaldehyde hydrazone

5. N'-Methoxycarbonyl-N'-3-iodopropargyl 4-chlorobenzaldehyde hydrazone

6. N'-Benzoyl-N'-3-iodopropargyl benzaldehyde hydrazone

7. N'-Methoxycarbonyl-N'-3-bromopropargyl 4-fluorobenzaldehyde hydrazone

8. N'-Methoxycarbonyl-N'-3-iodopropargyl 5-nitro-2-furancarboxaldehydehydrazone

9. N'-Methoxycarbonyl-N'-3-iodopropargyl 4-cyanobenzaldehyde hydrazone

10. N'-Methoxycarbonyl-N'-3-iodopropargyl 4-fluorobenzaldehyde hydrazone

11. N'-Methoxycarbonyl-N'-3-iodopropargyl 3,4-dichlorobenzaldehydehydrazone

12. N'-Benzoyl-N'-3-iodopropargyl 3-nitrobenzaldehyde hydrazone

13. N'-Ethoxycarbonyl-N'-3-iodopropargyl 3,4-dichlorobenzaldehydehydrazone

14. N'-Ethoxycarbonyl-N'-3-bromopropargyl 3,4-dichlorobenzaldehydehydrazone

15. N'-Methoxycarbonyl-N'-3-iodopropargyl 3,5-dichlorobenzaldehydehydrazone

16. N'-Methoxycarbonyl-N'-3-bromopropargyl 3,5-dichlorobenzaldehydehydrazone

The iodopropargyl compounds, i.e., those wherein X is I, are preferred.

As stated above, compositions comprising a compound according to formulaI and either an agronomically acceptable carrier, a cosmetic agent, acutting oil, a soap or synthetic detergent, a stabilizer, a film-formingmaterial, or the like have a wide range of utility for protectingagainst or controlling microorganisms from a wide variety of classesincluding fungus, bacteria, algae, viruses and yeasts. The preferredutilities of the compositions are to protect wood, paint, adhesive,glue, paper, textile, leather, plastics, cardboard, lubricants,cosmetics, food caulking, feed and industrial cooling water frommicroorganisms.

The following list specific industries and applications of the compoundsor compositions:

    ______________________________________                                        Industry            Application                                               ______________________________________                                        Adhesives, sealants adhesives                                                                     caulks                                                                        sealants                                                  Agriculture/food chain                                                                            adjuvant preservation                                                         agricultural active                                                           ingredient                                                                    agricultural chemical                                                         preservative                                                                  agricultural formulations                                                     preservation                                                                  animal feed preservation                                                      dairy chemicals                                                               fertilizer preservation                                                       food preservation                                                             food processing chemicals                                                     grain preservation                                                            post-harvest produce                                                          protection                                                                    sugar processing                                                              tobacco                                                   Construction products                                                                             asphalt/concrete                                                              cement modifiers                                                              construction products                                                         roof mastics                                                                  synthetic stucco                                                              wall mastics                                                                  joint cement                                              Cosmetics and toiletries                                                                          cosmetics                                                                     raw materials for                                                             cosmetics, toiletries                                                         toiletries                                                Disinfectants, antiseptics                                                                        antiseptic                                                                    disinfectant                                              Emulsions, dispersions                                                                            aqueous dispersions                                                           dispersed pigments                                                            latex                                                                         photographic emulsions                                                        pigment slurries                                                              polymer latices                                           Formulated consumer & industrial                                                                  air fresheners                                            products            fabric softeners                                                              hand cleaners                                                                 polishes, floor, furniture,                                                   shoe                                                                          sponges & towelettes                                                          spray strach                                                                  waxes                                                     Industrial processing, misc                                                                       dry cleaning fluids                                                           preservation                                                                  electrodeposition paint,                                                      baths, rinses.                                                                electrodeposition                                                             pre-treatment,                                                                post rinses                                                                   industrial fluids                                                             preservation                                                                  pasteurization baths                                                          process aid preservation                                  Industrial water treatment                                                                        air washers                                                                   cooling towers                                                                cooling water                                                                 water cooling                                             Laundry             household laundry                                                             products                                                                      laundered goods                                                               laundry wash water                                                            pre-washers                                                                   sanitizers-laundry                                                            removers, spot & stain                                    Leather, leather products                                                                         leather and hide                                                              leather and hide products                                 Lubricants, hydraulic aids                                                                        automotive lubricants and                                                     fluids                                                                        conveyor lubricants                                                           greases                                                                       hydraulic fluids                                                              hydraulic oils                                                                lubricants                                                Medical devices     diagnostic enzymes                                                            diagnostic kits                                                               medical devices                                           Metalworking & related app's                                                                      cutting fluids                                                                metal cleaning                                                                metalworking fluids                                       Odor control (active ingredient)                                                                  air conditioning                                                              animal bedding                                                                cat litter                                                                    chemical toilet prep'ns                                                       deodorizers                                                                   humidifiers                                                                   industrial deodorants                                                         sanitary formulations                                                         toilet bowls                                              Paints and coatings coating emulsions                                                             paints                                                    Paper and wood pulp, their products                                                               absorbant materials of                                                        paper and wood pulp                                                           packaging materials of                                                        paper and wood pulp                                                           paper                                                                         paper products                                                                paper treatment                                                               soap wrap                                                                     wood pulp                                                                     wood pulp products                                        Paper mill          paper mill slimicides                                                         pulp and paper slurries                                   Petroleum refining, fuels                                                                         aviation fuels (jet fuel,                                                     aviation gas)                                                                 burner, diesel and                                                            turbine fuel oils                                                             coal slurries                                                                 diesel fuel additives                                                         diesel fuels                                                                  fuels                                                                         gasoline                                                                      heating oils                                                                  hydrocarbons                                                                  kerosene                                                                      liquefied petroleum gas                                                       petrochemical feedstocks                                                      petroleum products,                                                           storage, transportation                                                       and production                                                                recycled petroleum                                                            products                                                                      residual fuel oils                                                            turbine oils                                              Photographic chemicals and process                                                                photographic processing -                                                     wash water, rinses                                                            photoplate processing                                                         chemicals                                                                     (developers, stabilizers                                                      etc)                                                      Printing            fountain solutions                                                            (printing)                                                                    ink components (pigments,                                                     resins, solvents, etc)                                                        inks                                                      Sanitizers (active) sanitizers                                                                    sanitizers-dairy                                                              sanitizers-dental                                                             sanitizers-fermentation                                                       sanitizers-food preparation                                                   sanitizers-food processing                                                    sanitizers-medical                                                            sanitizers-rendering                                                          sanitizers-veterinary                                     Soaps, detergents, cleaners                                                                       cleaners                                                                      detergents, hand automatic                                                    laundry, other                                                                industrial cleaners                                                           liquid soaps, hand, dish,                                                     laundry                                                                       oil and grease remover                                                        powdered soaps                                                                raw materials for cleaning                                                    products                                                                      soaps                                                                         surfactants                                               Textiles, textile products                                                                        bonded fabrics                                                                burlap                                                                        canvas                                                                        canvas goods                                                                  carpet backing                                                                carpets                                                                       clothing                                                                      coated fabrics                                                                curtains                                                                      draperies                                                                     engineering textiles                                                          fibers                                                                        geotextiles                                                                   goods made of textiles                                                        knitted fabrics                                                               nets                                                                          nonwoven fabrics                                                              rope                                                                          rugs                                                                          textile accessories                                                           textile products                                                              textiles                                                                      upholstery                                                                    woven fabrics                                                                 yarn                                                      Textile processing  dye fixatives                                                                 dyes                                                                          fiber lubricants                                                              hand modifiers                                                                sizes                                                                         textile processing fluids                                 Therapeutic (active or preservative)                                                              animal health/veterinary                                                      aquaculture                                                                   dental                                                                        human health                                                                  pharmaceutical/thera-                                                         peutic                                                    Water purification  charcoal beds                                                                 deionization resins                                                           filters                                                                       membranes                                                                     reverse osmosis                                                               membranes                                                                     ultrafilters                                                                  water purification                                                            water purification pipes,                                                     tubing                                                    Wood applications   lazures (wood stains)                                                         wood                                                                          wood products                                             Miscellaneous       alcohols                                                                      bedding incorporating                                                         water or gels                                                                 ceramic                                                                       contact lens cases-leaching                                                   electronic circuitry                                                          electronics chemicals                                                         enzymes-food production                                                       enzymes-industrial                                                            gel cushions                                                                  laboratory reagents                                                           marine antifoulants                                                           mildewcides                                                                   mining applications                                                           natural rubber latex                                                          oil field applications                                                        pipes                                                                         plastics                                                                      polymer systems                                                               polymers and resins                                                           (synthetic                                                                    and natural)                                                                  reagent preservation                                                          rubber                                                                        rubber products                                                               skin remover                                                                  solid protective/decorative                                                   films                                                                         swimming pools                                                                waste treatment                                                               water beds                                                ______________________________________                                    

The amounts of the compound to be used depend on the application. Theuseful amounts for a particular application are similar to amounts usedfor other microbicide compounds.

The compound can be used in combination with other microbicides. Theterm "microbicide" is considered equivalent to "antimicrobial" as usedherein.

Compounds of formula I can be prepared by a variety of methods. Onesuitable method comprises reacting a compound of formula II with aniodinating or brominating agent.

Suitable iodinating or brominating agents include, for example, iodine,bromine, an iodine-amino compound such as morpholine-iodine complex,morpholine-bromine complex, N-bromosuccinimide ("NBS") andN-iodosuccinimide ("NIS"), the latter being the most preferred.

When an iodine, bromine, or iodo-amino compound is used, base shouldalso be used, preferably sodium or potassium hydroxide, and solvent suchas methanol, ethanol, and aqueous ethanol should also be used.

When NIS or NBS is used, a catalyst such as, for example, silvernitrate, or the like, should be used in presence of solvent such asacetone, methyl ethyl ketone, tetrahydrofuran, and the like.

Reaction times of about 20 minutes to about 24 hours have been utilizedsuccessfully with reaction temperatures of about 0° C. to about 25° C.

Suitable methods of application of compounds of formula I to controlfungi, bacteria, algae, viruses, yeasts, and the like are in amounts andwith carriers, etc., as well known in the art.

The following examples are presented to illustrate a few embodiments ofthe invention. All parts and percentages are by weight unless otherwiseindicated.

Table (1) shows the structures and the physical data of the preferredrespective compounds.

                  TABLE 1                                                         ______________________________________                                        Physical Data                                                                  ##STR6##                                                                     No.     A           R'        X   Melting Point                               ______________________________________                                        1       4-ClPh      OMe       Br  102-105° C.                          2       4-ClPh      H         Br  135-140° C.                          3       Ph          OMe       I   149-151° C.                          4       4-MePh      OME       I   112-116° C.                          5       4-ClPh      OMe       I   143-146° C.                          6       Ph          Ph        I   109-111° C.                          7       4-FPh       OMe       Br  86-91° C.                            8       5-NO.sub.2 -furan                                                                         OMe       I   --                                          9       4-CNPh      OMe       I   126-132° C.                          10      4-FPh       OMe       I   --                                          11      3,4-Cl.sub.2Ph                                                                            OMe       I   110-118° C.                          12      3-NO.sub.2Ph                                                                              Ph        I   139-145° C.                          13      3,4-Cl.sub.2Ph                                                                            OEt       I   169-170° C.                          14      3,4-Cl.sub.2Ph                                                                            OEt       Br  148-149° C.                          15      3,5-Cl.sub.2Ph                                                                            OMe       I   183-184° C.                          16      3,5-Cl.sub.2Ph                                                                            OMe       Br  141-142° C.                          ______________________________________                                    

EXAMPLE 1 Preparation of N'-methoxycarbonyl-N'-3-bromopropargyl4-chlorobenzaldehyde hydrazone

To the suspension of N'-methoxycarbonyl 4-chlorobenzaldehyde hydrazone(4.0 g, 0.0188 mole) in dry acetone (50 ml) at room temperature undernitrogen was added potassium carbonate (3.9 g, 0.028 mole), followed bypropargyl bromide (3.4 g, 0.028 mole) with magnetic stirring. Thereaction mixture was refluxed for 24 hr. The reaction mixture was cooleddown to room temperature and was poured into water (200 ml). Theresultant precipitate was collected by suction-filtration affording 4.7g (99% yield) of N'-methoxycarbonyl-N'-propargyl 4-chlorobenzaldehydehydrazone, m.p.=102°-105° C. An NMR spectrum showed the desiredcompound.

This intermediate was used for the next step without furtherpurification.

To the suspension of N'-methoxycarbonyl-N'-propargyl4-chloro-benzaldehyde hydrazone (1.25 g, 0.005 mole) in dry acetone (40ml) at room temperature with magnetic stirring was addedN-bromo-succinimide (1.03 g, 0.0058 mole), followed by silver nitrate(0.011 g, 0.00065 mole). The reaction mixture was stirred at roomtemperature for 1 hr. The purple reaction mixture was poured into waterand the resultant precipitate was collected by suction-filtration togive a crude product. The crude product was dissolved in ethyl acetate(50 ml), dried over anhydrous sodium sulfate, and filtered to get acolorless solution. The solvent was evaporated on a rotary evaporatoraffording 1.10 g (67.1% yield) of N'methoxycarbonyl-N'-3-bromopropargyl4-chloro-benzaldehyde hydrazone as a solid. m.p.=102°-105° C. An NMRspectrum showed the desired compound.

EXAMPLE 2 Biocidal Evaluations of Compounds

A minimum inhibitory concentration (MIC) value is obtained using abroth, two-fold serial dilution test performed as follows: A stocksolution of dispersion of the test compound, typically at aconcentration of 1%, is made in a 5:3:2 solvent solution of acetone,methanol, and water. A volume of the stock solution is dispensed intoculture media to give an initial starting test concentration of 500 ppmcompound.

The test is carried out by adding and equal volume of broth to eachvessel in the dilution series, except for the first vessel. The firstvessel contains twice the volume of broth plus the initial concentrationof test compound. One half of the broth from the first vessel istransferred to the second vessel. After being mixed, one half theresulting volume is removed from the second vessel and transferred tothe third vessel. The entire cycle is repeated sufficiently to give aseries of concentrations amounting to 500, 250, 125, 63, 31, 16, 8, and4 ppm (or 100, 50, 25, 12.5, 6.2, 3.1, 1.6, and 0.8), respectively.

Each vessel is then inoculated with a cell suspension of the appropriatetest organism. Bacteria are grown in both and fungi on agar slats for atime and at a temperature appropriate to the species being tested. Atthe end of the growth period, the broth is vortexed to disperse thecells. In the case of fungi, the pores are harvested by pipetting wateronto the slant and dislodging the spores with a sterile loop. Thecell/spore suspension is standardized by controlling incubation time,temperature, and the volume of the diluent. The suspension is then usedto inoculate the vessels containing the broth compound. The vessels arethen incubated at the appropriate temperature. After the incubation, thevessels are examined for growth/no growth. The minimum inhibitoryconcentration (MIC) is defined as the lowest concentration of compoundthat results in complete inhibition of growth of the test organism.

The organisms tested to demonstrate biocidal activity include:

BACTERIA

Pseudomonas fluorescens (Psfl)

Pseudomonas aerugenosa (Psae)

Escherichia coli (Ecol)

Staphylococcus aureus (Saur)

FUNGI

Aspergillus niger (Anig)

Aureobasidium pullulans (Apul)

                  TABLE 2                                                         ______________________________________                                        Biocidal Evaluation                                                           The Result of Minimum Inhibitory Concentration (MIC) Tests                           MIC (ppm)                                                              Compound #                                                                             Psfl    Psae    Ecol  Saur  Anig  Apul                               ______________________________________                                        1        >500     250    >500  >500  >500    63                               2        >500     250    >500  >500  >500    63                               3        >500     250    >500   125   <4    <4                                4         125     125     250    16   <4     8                                5         125      16     125    8    <4    <4                                6          50      25      50    50    6     3                                7         125      31     125    63    31    31                               8         250     125      63   <4    <4    <4                                9        >500    >500    >500  >500  >250  --                                 10       >500    >500    >500   <4    <4     <4                               11       >500    >500    >500    8    <4    <4                                12       >100    >100    >100  >100  >100   100                               13       >100    >100    >100  >100   100  >100                               14       >100    >100    >100  >100  >100  >100                               15       >100    >100    >100  >100  >100  >100                               16       >100    >100    >100  >100  >100  >100                               ______________________________________                                    

EXAMPLE 3 In-Vitro Plant Fungicide Tests of Compounds

The organisms employed in the test are:

    ______________________________________                                        PYU         Pythium ultimum (Oomycete)                                        PHY         Phytophthora capsici (Oomycete)                                   PIR         Piricularia oryzae (Ascomycete)                                   HEL         Cochliobolus sativus (Ascomycete)                                 BOC         Botrytis cinerea (Ascomycete)                                     FUS         Fusarium roseum (Ascomycete)                                      SEP         Septoria nodorum (Ascomycete)                                     RHI         Rhizoctonia solani (Basidiomycete)                                XAN         Xanthomonas campestris (basterium)                                ______________________________________                                    

METHODS

1. Culture maintenance: Transfers in steps 1 and 2 are done in a laminarflow hood. All 8 fungi and the bacterium used in this test aretransferred and maintained on potato dextrose agar plates each week (2plates/organism). Organisms are used when they are the following ages:a. 1 week old: PYU, PHY, RHI; b. 2 weeks old: XAN, PIR, BOC, HEL, FUS,SEP. Pythium ultimum and Phytophthora capsici are transferred toasparagine-sucrose broth shake cultures (ASB). Rhizoctonia solani,Fusarium roseum, and Zanthomonas campestris are maintained in yeastextract-dextrose broth (YDB) on a shaker. Culture flasks are inoculatedwith 6 mycelial plugs each (except for Pythium which is inoculated withonly 3 plugs) taken from PDA plates. All liquid shaker cultures are usedafter 2 days growth.

2. Inoculum preparation. Conidia and mycelium from PIR, BOC, HEL, andSEP, are lightly scraped off into YDB so that mostly conidia are used asinoculum. The conidial suspension is strained through a double layer ofcheesecloth to remove mycelial clumps. One plate products enough conidiaor mycelium to inoculate 100 ml of YDB. XAN broth cultures is poured (1ml culture/100 ml broth) into YDB. PYU, PHY, RHI and FUS cultures areground up (2-3 5 second burst in a blender) and all but Pythium andPhytophthora are filtered through a double layer of sterile cheeseclothto remove large mycelial clumps. Ten ml of the culture solutions of R.solani and F. roseum are added to 90 ml of YSP and 10 ml of the P.capsici is added to 90 ml ASB. Two ml of the culture solution of P.ultimum is added to 98 ml of ASB. Care must be made not to overinoculate(e.g. solutions should appear fairly clear to the eye, yet when held upto light a faint cloudiness should be visible) or standards will notbehave properly. The inoculum mixtures are place in microtiter platesusing a 12-tipped pipet. 175 μl (single dose) or 100 μl (dose-responsetest) of inoculum broth is placed in each well of the microtiter plates.The plates with inoculated media are placed in the refrigeratorovernight. There are two replications per treatment.

3. Addition of compounds. This operation is carried out in a chemistryhood. Sic microtiter plates have 245 microliters of sterile water addedto their wells ahead of time. 10 Mg a.i. of the compounds are placed in1 ml 1:1 acetone:methanol. 5 Microliters of this solution is pipettedinto the microtiter plates containing the sterile water according to thegrid. There are 45 compounds and 3 scattered control treatments perplate. There are 2 replicates per treatment. 25 Microliters of solutionis transferred to the inoculated plates with a 96 well replicator. Thereplicator is flame sterilized with alcohol, rinsed with sterile water,and blotted on sterile paper towels between each transfer.

                                      TABLE 3                                     __________________________________________________________________________    The Results of In-Vitro Plant Fungicide Tests                                 Rate      % Control                                                           Compound                                                                            (PPM)                                                                             BOC FUS HEL PHY PIR PYU RHI SEP XAN                                 __________________________________________________________________________    1     25  0   0   0   0   0   0   0   --  0                                   2     25  0   0   0   75  50  0   0   --  0                                   3     25  0   75  0   75  0   75  100 --  0                                         50  0   100 0   100 95  100 100 75  0                                   4     --  --  --  --  --  --  --  --  --  --                                  5     25  0   95  100 50  100 50  75  --  0                                   6     25  0   0   0   100 100 100 0   100 0                                   7     25  0   0   0   0   0   0   0   100 0                                         50  0   0   0   90  90  100 0   0   0                                   8     50  0   100 100 100 100 100 100 100 0                                         50  0   100 100 0   100 --  100 100 0                                   9     50  50  100 100 95  100 100 100 100 0                                   10    50  0   100 100 100 100 100 100 100 0                                   11    50  50  100 100 90  100 0   100 90  0                                   12    50  0   0   0   0   100 0   95  0   0                                   13    25  0   75  50  0   100 0   90  50  0                                   14    25  0   0   0   0   0   0   50  0   0                                   15    25  0   75  50  0   100 0   75  0   0                                   16    25  0   0   0   0   0   0   0   0   0                                   __________________________________________________________________________

EXAMPLE 6 Agricultural Fungicide Evaluations of Compounds

The compounds of this invention were tested for fungicidal activity invivo against cucumber downy mildew (CDM), rice blast (RB), Septoriaglume blotch of wheat (SNW), tomato late blight (TLB), wheat powderymildew (WPM) and wheat leaf rust (WLR) and the results are shown inTable 4. In tests on cereals (except for rice plants used for testingrice blast), the plants are trimmed about 24 hours prior to theapplication of the fungicide compound to provide a uniform plant heightand to facilitate uniform application of the compound and inoculationwith the fungus. The compounds were dissolved in a 2:1:1 mixture ofwater, acetone, and methanol, sprayed onto the plants, allowed to dry(four to six hours), and then the plants were inoculated with thefungus. Each test utilized control plants which were sprayed with thewater, acetone, and methanol mixture and inoculated with the fungus. Theremainder of the technique of each of the tests is given below and theresults are reported as percent disease control (percentages of plantstreated with the compounds of the present invention lacking diseasesigns or symptoms compared to the untreated control plants).

Cucumber Downy Mildew (CDM)

Pseudoperonospora cubensis was maintained on leaves of live Marketercucumber plants in a constant temperature room at 65° F. to 75° F. inhumid air with moderate light intensity for 7 to 8 days. A watersuspension of the spores from infested leaves was obtained and the sporeconcentration was adjusted to about 100,000 per ml of water.

Marketer cucumber seedlings were inoculated by spraying the underside ofthe leaves with a DeVilbiss atomizer until small droplets were observedon the leaves. The inoculated plants were incubated in a mist chamberfor 24 hours at about 70° F. and then subsequently incubated for 6 to 7days in a controlled temperature room under mist at 65° F. to 75° F.Seven days after inoculation, the percent disease control wasdetermined.

Rice Blast (RB)

Nato rice plants were inoculated with Piricularia oryzae (about 20,000conidia per ml) by spraying the leaves and stems with an airbrush untila uniform film of inoculum was observed on the leaves. The inoculatedplants were incubated in a humid environment (75° F. to 85° F.) forabout 24 hours, then placed in a greenhouse environment (70° F. to 75°F.). Seven to eight days after inoculation, the percent disease controlwas determined.

Tomato Late Blight (TLB)

Phytophthora infestans was cultured on four week old Pixie tomato plantsin a controlled environment room (65° F. to 70° F. and 100% relativehumidity). After storage, the spores were washed from the leaves withwater and dispersed by DeVilbiss atomizer over three week old Pixietomato plants which had been sprayed previously with experimentalfungicides. The inoculated plants were placed in a humidity cabinet at70° F. and constant mist for 24 hours for infection. The plants werethen moved to the controlled environment room as above and scored afterthree more days incubation. Disease control levels were recorded aspercent control four days after inoculation and five days after sprayingthe compounds.

Wheat Powdery Mildew (WPM)

Erysiphe graminis (f. sp. tritici) was cultured on Pennol wheatseedlings in a controlled temperature room at 65° F. to 75° F. Mildewspores were shaken from the culture plants onto Pennol wheat seedlingswhich had been sprayed previously with the fungicide compound. Theinoculated seedlings were kept in a controlled temperature room at 65°F. to 75° F. and subirrigated. The percent disease control was rated 8to 10 days after the inoculation.

Wheat Leaf Rust (WLR)

Puccinia recondita (f. sp. tritici Races PKB and PLD) was cultured onseven day old wheat (cultivar Fielder) over a 14 day period in thegreenhouse. Spores were collected from the leaves with a cyclone vacuumor by settling on aluminum foil. The spores were cleaned by sievingthrough a 250 micron opening screen and stored or used fresh. Storageemployed sealed bags in an Ultralow freezer. When stored, spores must beheat shocked for two minutes at 40° F. before use. A spore suspension isprepared from dry uredia by adding 20 mg (9.5 million) per ml of Soltroloil. The suspension is dispensed into gelatin capsules (0.7 ml capacity)which attache to the oil atomizers. One capsule is used per flat oftwenty of the two inch square pots of seven day old Fielder wheat. Afterwaiting for at least 15 minutes for the oil to evaporate from the wheatleaves, the plants are placed in a dark mist chamber (18°-20° C. and100% relative humidity) for 24 hours. The plants are then put in thegreenhouse for the latent period and scored after 10 days for diseaselevels. Protective and curative tests were inoculated one day after andtwo days, respectively, before spraying the plants with the testchemicals.

                  TABLE 4                                                         ______________________________________                                        Green House Test Results of Plant Diseases Control                            Com-   Rate    % Control                                                      pound  (ppm)   CDM     RB   SNW   TLB  WLR   WPM                              ______________________________________                                        1      --      --      --   --    --   --    --                               2      600     --      --   --    50   0     0                                3      200     99      90   --    80   50    50                               4      200     95      90   50    80   50    0                                5      200     99      95   0     90   80    0                                6      --      --      --   --    --   --    --                               7      200      0       0   0     0    0     0                                8      200      0      90   0     0    0     0                                9      200     85       0   0     0    0     0                                10     200     50      50   0     0    0     50                               11     200     95      90   0     80   --    0                                12     --      --      --   --    --   --    --                               13     200     85       0   0     0    50    50                               14     200      0       0   0     0    0     85                               15     200      0       0   0     0    0     0                                16     200      0       0   0     0    0     0                                ______________________________________                                    

What is claimed is:
 1. A compound of the formula ##STR7## wherein A isselected from the group consisting of (1) phenyl, (2) naphthyl, (3)phenyl substituted with one or more halo, cyano, (C₁ -C₄)alkyl, nitro,(C₁ -C₄)haloalkyl, and (C₁ -C₄)thioalkyl, (4) naphthyl substituted withone or more halo, cyano, (C₁ -C₄)alkyl, nitro, (C₁ -C₄)haloalkyl, and(C₁ -C₄)thioalkyl, (5) thiophene, (6) furan, (7) thiophene substitutedwith one or more substituents selected from halo and nitro, and (8)furan substituted with one or more substituents selected from halo andnitro;R is selected from the group consisting of hydrogen, (C₁ -C₄)alkyland substituted or unsubstituted phenyl wherein the substituents areselected from one or more halo, cyano, (C₁ -C₄)alkyl, nitro, (C₁-C₄)haloalkyl, and (C₁ -C₄)thioalkyl; R¹ is selected from the groupconsisting of (C₁ -C₄) alkoxy hydrogen; optionally substituted phenylwherein the phenyl substituents are selected from the group consistingof halo,cyano, (C₁ -C₄)alkyl, nitro, (C₁ -C₄)haloalkyl, and (C₁-C₄)thioalkyl; (C₁ -C₈) alkyl; and optionally substituted heterocycleswherein said heterocycles are selected from the group consisting ofthiophene, furan, imidazole, and triazole, which are optionallysubstituted with (C₁ -C₃)alkyl, halo, and nitro; and X is selected fromthe group consisting of I and Br.
 2. Compound according to claim 1wherein A is selected from the group consisting of phenyl, phenylsubstituted with halo or nitro, and furan substituted with nitro. 3.Compound according to claim 2 wherein X is I.
 4. Compound according toclaim 1 wherein R is hydrogen and R¹ is selected from the groupconsisting of hydrogen, (C₁ -C₄)alkoxy, and phenyl.
 5. Compoundaccording to claim 1 wherein A is selected from the group consisting ofphenyl, phenyl substituted with halo or nitro, and furan substitutedwith nitro; R is hydrogen; R¹ is selected from the group consisting ofhydrogen, (C₁ -C₄)alkoxy, and phenyl; and X is I.
 6. Compound accordingto claim 1 selected from the group consisting ofN'-methoxycarbonyl-N'-3-bromopropargyl 4-chloro-benzaldehyde hydrazone;N'-formyl-N'-3-bromopropargyl 4-chlorobenzaldehyde hydrazone;N'-methoxycarbonyl-N'-3-iodopropargyl benzaldehyde hydrazone;N'-methoxycarbonyl-N'-3-iodopropargyl 4-methylbenzaldehyde hydrazone;N'-methoxycarbonyl-N'-3-iodopropargyl 4-chlorobenzaldehyde hydrazone;N'-benzoyl-N'-3-iodopropargyl benzaldehyde hydrazone;N'-methoxycarbonyl-N'-3-bromopropargyl 4-fluorobenzaldehyde hydrazone;N'-methoxycarbonyl-N'-3-iodopropargyl 5-nitro-2-furancarboxaldehydehydrazone; N'-methoxycarbonyl-N'-3-iodopropargyl 4-cyanobenzaldehydehydrazone; N'-methoxycarbonyl-N'-3-iodopropargyl 4-fluorobenzaldehydehydrazone; N'-methoxycarbonyl-N'-3-iodopropargyl3,4-dichlorobenzaldehyde hydrazone; N'-benzoyl-N'-3-iodopropargyl3-nitrobenzaldehyde hydrazone; N'-ethoxycarbonyl-N'-3-iodopropargyl3,4-dichlorobenzaldehyde hydrazone;N'-ethoxycarbonyl-N'-3-bromopropargyl 3,4-dichlorobenzaldehydehydrazone; N'-methoxycarbonyl-N'-3-iodopropargyl3,5-dichlorobenzaldehyde hydrazone;N'-methoxycarbonyl-N'-3-bromopropargyl 3,5-dichlorobenzaldehydehydrazone.
 7. Composition comprising a compound according to claim 1 andan agronomically acceptable carrier.
 8. Composition comprising acompound according to claim 1 and a stabilizer.